Resin compositions comprising a segmented fluorine-containing copolymer and an aminoplast



United States Patent RESiN COMPGSITIONS COPViFRl-Sl'ldfi A MENTEDFLUfiRlNE-CGNTAINEJG COEPOL- YMER AND AN AMENGPLAST Archibald N.Bolstad, Afton Township, Washington County, Patsy G. Sherman,Bloornirrgton, and Samuel Smith, Roseville, Minn, assignors to MinnesotaMining and Manufacturing Company, St. Paul, Mind, a corporation ofDelaware No Drawing. Filed Dec. 14 1962, Ser. No. 243,642 Claims. (Cl.26il29.4)

This application is a continuation-in-part of Serial No. 832,490, filedAugust 10, 1959, now Patent No. 3,068,187.

This invention relates to new and useful segmented fluorine-containingcopolymers in combination with triazine formaldehyde resins and to thetreatment of textiles therewith.

Fluorine-containing polymers are known to be effective materials fortreating substrates, e.g. US. Patent 2,803,- 615, wherein it wasrealized that durability would be enhanced by applying a polymer. In thepresent invention it has been discovered that certain segmentedfluorinecontaining copolymers are at least as effective and have uniqueadvantages of their own wherein their solubility characteristics arematerially altered and durability of surface treatments is materiallyenhanced over previous polymers. This enhanced durability is especiallyimportant where cleaning operations are required, such as in thetreatment of decorative and apparel fabrics, leather jackets and coatsand painted surfaces. The durability requirements for apparel fabrics isparticularly stringent in those articles which are frequently launderedor dry cleaned. Fabrics of this nature which have been treated with thesegmented copolymers of this invention are very durable in that thesurface properties imparted to the fabrics remain almost unaffectedafter long wear and successive dry cleanings and launderings.

The segmented copolymers of this invention have at least onefluorine-containing segment, hereinafter referred to as Segment A,comprising at least four fluorine-containing monomeric units,hereinafter referred to as a units, having a perfiuoroalkyl group of thegeneral formula C Fz where n is at least 4 and less than 20 (preferably5 to Segment A contains at least 30 percent and up to 75 percent(preferably 40 to 70 percent) by weight of fluorine derived from theperfiuoroalkyl group. The remaining segments, hereinafter referred to asSegment B, are comprised principally of polymerized monomeric units ofan ethylenically unsaturated monomer, hereinafter referred to as 12units, different from the a units of Segment A. Segment B is made up ofat least 5 consecutive b units and contains less than 10 percent(preferably from O to 5 per-cent) by weight of fluorine in C F groupswhere n is as stated above. For purposes of illustrating the invention,such segmented copolymers can be represented by the generic formula:

(Segment A) (Segment B) where m and p are integers, Segment A is from0.5 to 80 percent by weight of the macromolecule and Segment B is fromto 99.5 percent by Weight of the macromolecule.

These segmented copolymers may also be represented by the genericformula showing their monomeric units as follows:

where a and b units are as defined above;

It is at least 4; v is 0 or an integer such that the weight of (b) unitsrepresents less than 26% by weight of [(a) (b),,] (Segment A);

w is 0 or an integer such that the weight of (a) units represents lessthan 20 percent by weight of )w( )x]z (Segment B); x is at least 5; andy and z are integers.

Generally speaking, the segmented copolymers are block and graftcopolymers which contain a plurality of segments. in block copolymersthe segments are present in a linear molecule; while in graft copolymersthe segments of one polymerized species are primarily present as rancheson a backbone of the dissimilar polymerized species.

These segmented copolymers are to be distinguished from homogeneouscopolymers. The term homogeneous copolymers as employed in thisspecification is one in which the component monomeric units appear in amore or less random or alternating fashion, and such molecules arecharacterized by the fact that no more than one of the component monomerspecies is present in long, unbroken sequences in any one macromolecule.Homogenous copolymers embrace substantially all normal copolymercompositions.

The distribution of the monomeric units in such copolymers is governedby the monomer relative reactivity ratios and the monomer concentrationsexisting at the time of polymerization. The definition of relativereactivity ratio is the ratio of the rate at which a growing copolymerchain adds the same monomer which is prescut as the active terminal unitto the rate at which the same terminal unit adds the dissimilar monomerwhen the monomers are present at equimolar concentrations.

Segmented copolymers are highly heterogeneous. Whereas the distributionof monomeric units within the individual segments may be governed bythemonomer relative reactivity ratios and their concentrations at thetime in which the individual segments are formed, these parameters donot afiect the frequency or position in which the segments chemicallybond within the macromolecule.

Homogeneous copolymers have properties which are generally intermediatebetween the properties of the homopolymers of the component monomers.The properties of the homogeneous copolymers, as a general rule, changein direct proportion to monomer composition, e.g. styrene-butadienecopolymers. It has been found, however, that having chemicallydissimilar segments bonded together within the macromolecule bestowscertain uniquely useful properties to the segmented copolymers of thisinvention which are not possessed by analog-- ous homogeneouscopolymers.

These segmented copolymers are useful for imparting repellency to oiland water and resistance to soiling to a variety of substrates. Fibrous,porous and continuous surfaces may be treated with these segmentedpolymers to achieve these results. Illustrative articles to be treatedare textiles, glass, paper, Wood, leather, fur, asbestos, bricks,concrete, metals, ceramics, plastics, painted surfaces and plaster.Because of advantages incident to the repellency to oil and water andtheir resistance to soiling imparted by coating them with the segmentedcopolymers of this invention, preferred classes of articles to betreated are textile apparel, upholstery, draperies, carpeting, paperbags, cardboard container-s, luggage, handbags, shoes, jackets, redwood,pine, cedar, and asbestos siding materials, bricks, concrete, floor orwall tiles, painted or unpainted metals, such as appliances andautomobile bodies, masonry, wood, plaster, wallpaper and wallboardsurfaces. In the treatment of fabrics, 0.05 to 5% (preferably 0.1 to 1%)by weight segmented copolymer based on the weight of the fabricproducesdesirable surface properties. Illustrative textiles which can beadvantageously treated with the segmented copolymers of this inventionare those based on natural fibers, e.g. cotton, wool, mohair, linen,jute, silk, ramie, sisal, kenaf, etc. and those based on syntheticfibers, e.g. rayon, acetate, acrylic, polyester, saran, azylon, nytril,nylon, spandex, vinal, olefin, vinyon and glass fibers. (The abovedesignations of synthetic fibers are the proposed generic terms set upby the Federal Trade Commission.) The treatment of these fabrics withthe compositions of this invention imparts no adverse effect on the handof the fabric and in some cases has a softening effect, therebyimproving the hand.

The segmented copolymers of this invention may be applied as a surfacetreatment by known methods of coating such as spraying, brushing orimpregnation from an aqueous or organic solvent dispersion or an organicsolvent solution of the segmented copolymer. The segmented copolymer maybe used as the sole component in the treating vehicle or as a componentin a complex multiingredient formulation. For instance, excellent waterand oil repellency and soil resistance is obtained on textile fabricswhich are treated simultaneously with the segmented copolymer andconventional finishes, such as mildew preventatives, moth resistingagents, crease resistant resins, lubricants, softeners, sizes, flameretardants, antistatic agents, dye fixatives, and water repellents. Inthe treatment of paper the segmented copolymer may be present as aningredient in a wax, starch, casein, elastomer or Wet strength resinformulation. By mixing the segmented copolymer in an aqueous or oil typepaint formulation it may be applied effectively to unpainted or previously painted asbestos siding, wood, metal and masonry. In the treatment offloors and tile surfaces and like substrates the segmented copolymer maybe applied by incorporating it in a wax based emulsion or solution.

. In addition to oil and Water repellency and soil resistanceproperties, the segmented copolymers may be used to impart lower surfaceadhesion values and lower coefiicients of friction to substrates.Accordingly, they may also be used as mold release agents and relatedapplications.

The segmented copolymers of this invention can, in general, bedistinguished from the three classes of polymeric materials containing amonomer units known to the prior art (namely homopolymers, mixedpolymers and homogeneous copolymers) by reference to their difference inphysical and solubility characteristics and their effectiveness insurface treatments. The fluorine-containing homopolymers arecharacterized by their solubility in fluorine-containing solvents suchas the fluoroalkanes, fluorochloroalkanes, fiuoroalkyl substitutedaromatics, and alkyl esters of perfiuoroalkanoic acids, and theirgeneral insolubility in common organic solvents such as aromatics,chlorinated alkanes and aromatics, ketones, esters, and ethers. Thesesolubility characteristics greatly limit their application in solventcoating formulations because of the high cost and in many cases the highvolatility of the fluorinated solvents. These homopolymers are alsocharacterized by the efiiective oil and Water repellency and soilresistant properties which they impart to surfaces. However, economicalutilization of the fluorine-containing homopolymers is restricted inmany applications by their relatively high cost and the necessity forusing about 1 percent by weight of the homopolymer on the surfaces toobtain effective treatments.

The mixed polymers, i.e. a mechanical blend or a mixture of dispersionsof a homopolymer containing i1 units with a polymer containing only bunits, are characterized by the fact that they are incompatible mixturesand cannot be codissolved in any useful treating solvent. In some cases,these mixed polymers give effective surface treatments when applied fromaqueous dispersions, but surfaces treated with the mixed polymer arecharacterized by relatively poor durability characteristics as comparedto surfaces treated with the segmented copolymers of this invention.

The homogeneous copolymers of a and b units have physical and solubilityproperties greatly different from the homopolymer of 11 units. However,when a sufiicient amount of b units are incorporate into the copolymerto bring about a material cost reduction or any significant improvementin physical or solubility properties, a noticeable impairment of theoleophobic and hydrophobic properties and their degree of durability ontreated surfaces results.

The segmented copolymers are characterized by the fact that they giveeffective surface treatments over a wide composition range. Thesegmented copolymers are further characterized by the fact that desiredsolubility and physical properties can be obtained by varying the bunits in the segments of themacromolecule. Thus, certain segmentedcopolymers comprising substantial Weights of segments based on butadieneor chloroprene are soluble in aromatic solvents and chlorinated alkanes.Moreover, these products are characterized by high degrees offlexibility and abrasion resistance. The use of styrene as the base forthe formation of B segments provides a product having increased hardnessand softening temperature and solubility in benzene. The use of methylvinyl ketone in the formation of B segments gives a product of greattoughness and solubility in dioxane and acetone.

Because of the wide latitude available in the selection of one or more bmonomers suitable for the formation of at least one B segment in themacromolecules of this invention, it becomes apparent that segmentedcopolymers can be made which have essentially any desired physical orsolubility property built into the compound. The inclusion of A segmentscomprising a monomer units in such macromolecules imparts surfacecharacteristics to the compounds which are superior in many respects tothose shown by the analogous fluorine-containing homopolymers. Forexample, the durability of the surface characteristics of fabricstreated with the segmented copolymers of this invention to wear, drycleaning, and laundering are greatly enhanced.

The cost of surface treatments is almost directly related to the percentof fluorine derived from the a units deposited on the surface. Since thesegmented copolymers inherently contain less fluorine than the analogoushomopolymers of the a units and can frequently be employed atsubstantially lower treatment levels, a material savings in cost can beaccomplished by the practice of this invention.

The desired surface characteristics of the segmented copolymers of thisinvention become evident when the weight of A segments Within themacromolecule constitutes as little as 0.5 percent by weight of thetotal molecular weight. The advantages of this novel class of compoundsas contrasted to the homopolymer of (1 units disappears when the weightof the A segments approaches about percent of the total molecularweight. A preferred series of compositions for the treatment of fabricsreside in the range where the A segment constitutes 3060 percent byweight of the macromolecule.

The segmented copolymers of this invention can be prepared by severalprocesses. In general, the conditions required for their preparation arethe formation of either A or B segments as a prepolymer which eitherparticipates by initiation or chain transfer mechanisms in, thesubsequent polymerization reaction in which the dissimilar segments areformed, or is chemically bonded to the previously formed dissimilarsegments in a subsequent chemical reaction. The prepolymer may be apolymer in which one or more of the monomeric units contain functionalgroups which participate in initiation or chain transfer mechanisms inpolymerization reactions.

Conjugated dienes are especially useful for providing 1; units since Bsegments based on conjugated dienes readily combine with A segmentsduring the formation of the A segments. Polymers which inherently do nottend to participate in further polymerization reactions may be employedas prepolymers by incorporation, via copolymerization, of a monomerhaving functional groups which participate by providing initiation orchain transfer sites. The functional group may also be incorporated bychemical or physical modification of the prepolymer, such as byperoxidation, bromination, mastication and irradiation.

Usually, the prepolymer is prepared in the absence of the dissimilarmonomer as a first step in the formation of the segmented copolymers.However, in cases where the a and b monomers have Widely differentrelative reactivity ratios (e.g. one monomer has a value of greater than1, while the other monomer has a value of less than 0.1) and the morereactive monomer forms a segment inherently containing functional groupscapable for participating in subsequent polymerization reactions, thensuch monomers can be polymerized simultaneously to produce the segmentedcopolymers of our invention. Thus, chloroprene and CF (Cl-' SO N (CH CHCH CH OCOC (CH =CH having relative reactivity ratios of about 16 and 0,respectively, can be simultaneously copolymerized in the weight ratiosof 2575 percent chloroprene to 75-25 percent CF (CR SO N (CH CH CH CHOCOC (CH =CH (mol ratios:7 1-96 chloroprene: 294% CF (CF 7SO2N (CH CH CHCH OCOC (CH =C-H to produce segmented copolymers which are particularlyvaluable. The segmented copolymers produced in these reactions consistof A segments containing at least 80 percent by weight of CE, CF SO N CHCH CH CH OCOC (CH =CH units and B segments containing at least 80percent by weight of chloroprene units. The fact that these products aresegmented copolymers is demonstrated by their solubility and surfacecharacteristics. When prepared with mercaptan modifiers to avoid polymercrosslinking, the products are completely soluble in xylenehexafiuoride, benzene and clflorinated alkanes. (These same solvents canbe used to separate quantitatively mixtures of the homopolymers ofchloroprene and In addition, the fabric treating results of thesegmented copolymer made in this direct fashion are virtuallyindistinguishable from the results obtained with a segmented copolymermade by polymerizing C1 (CF SO N (CH CH CH CH OCOC (CH =CH in thepresence of the prepolymer of chloroprene.

The general structural formula of the fluorine-containing monomersemployed in this invention is RfP where R; is a perfluoroalkyl radicalof the formula C F where n is at least 4 and less than 20 (preferably 5to and P is a radical containing a polymerizable group. lllustrativetypes of these fluorine-containing monomers are the acrylate,methacrylate and tX-ChIOl'O acrylate esters of N-alkanolperfiuoroallrane sulfonamides, l,1-dihydroperfluoroallranols,omega-perfiuoroalkyl alkanols and 1,1,3- trihydroperfiuoroalkanols,l,l-dihydroperfiuoroalkyl acrylamides, l,l-dihydroperfiuoroalkyl vinylethers, vinyl perfluoroalkyl ketones, allyl perfiuoroalkyl ketones,l-perfluoroalkenes, 2-perfluoroalkyl ethylenes,1,1-dihydroperfluoroalkene-l, perfiuoroalkyl substituted styrenes, andvinyl and allyl esters of perfiuoroalkanoic acids.

Illustrative ethylenically unsaturated monomers which may be employed toform a segmented copolymer with the above fluorine-containing monomersare ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidenechloride, vinylidene fluoride, vinyl chloroacetate, acrylonitrile,vinylidene cyanide, styrene, alkylated styrenes, sulfonated styrenes,halogenated styrenes, acrylic acid and alkyl esters thereof, methacrylicacid and alkyl esters thereof, alpha-chloroacrylic acid and alkyl estersthereof, methacrylonitrile, acrylamide, methacrylamide, vinyl carbazole,vinyl pyrrolidone, vinyl pyridine, vinyl alkyl ethers, vinyl alkylketones, butadiene, chloroprene, fluoroprene and isoprene. Functionalgroups which will participate as initiating or chain transfer sitesinclude thiol, disulfide, chloro, bromo and iodo groups, peroxide andhydroperoxide groups, and activated hydrogen atoms (e.g. tertiaryallylic hydrogens). I

Generally speaking, the segmented copolymers of this invention contain a11101 ratio of b units to a units of at least 5 to 2 (preferably atleast 5 to l), and the ethylenically unsaturated monomers are combinedin segments which contain at least 5 consecutive units of theethylenically unsaturated monomeric units (preferably at least 20).

The segmented copolymers of this invention may be prepared in anemulsion system to produce latices which may be utilized directly totreat substrates in accordance with the teachings of this invention. Thecopending application of Sherman and Smith, S.N. 650,294, filed August3, 1957, now Patent No. 3,062,765, describes a process for the emulsionpolymerization which may be employed to prepare the latices. In caseswhere the copolymers are utilized in an organic solvent system, they maybe polymerized in the solvent or recovered from the latex, such as bycoagulation, and dissolved in the solvent. Illustrative solvents areperchloroethylene, benzene, acetone, butyl acetate and dioxane.

Anionic, cationic, or non-ionic emulsifiers and blends of non-ionicemulsifiers with either anionic or cationic emulsifiers may beincorporated in the latices of this invention. The blends of cationicand non-ionic emulsifiers have been found-to be useful where thecomposition is employed to treat textiles and like substrates.

Antioxidants may also be added to the polymer compositions. Theseantioxidants function primarily to stabilize the polymer itself and aremost useful in segmented copolymers based on conjugated dienes whichotherwise tend to oxidize and discolor and may adversely affect thesubstrate.

In the treatment of fabrics, the segmented copolymers of this inventionmay be applied in admixture with other treating agents, such as creaseresisting resins, sizes, softeners, and water repellents. Known treatingagents of these classes are as follows.

Crease resisting resins: urea-formaldehyde resins, ethyleneurea-formaldehyde resins, melamine-formaldehyde resins,triazone-formaldehyde resins, epoxy resins, and polyglycol acetals.

Sizes: starch, casein, glue, polyvinyl alcohol, polyvinyl acetate,methyl cellulose, carboxymethyl cellulose. Softeners: polyethyleneglycols, polyethylene, dimethyl polysiloxanes, amines and amides derivedfrom fatty acids and ethylene oxide condensation products of such aminesand amides.

Water repellents: waxes, aluminum salts of fatty acids,

silicone resins, chromium complexes of fatty acids, N- alkyl amidomethylpyridinium salts, and melamineformaldehyde resin condensates with amidesfrom fatty acids.

This invention may be illustrated further by reference to the followingexamples in which all parts are expressed as parts by weight and allpercentages are expressed as percent by weight, unless specifiedotherwise.

The fluorine-containing monomers, procedure for preparing the segmentedcopolymers, and the method for evaluating their effectiveness were asfollows except as otherwise indicated:

The fluorinated monomers employed in the examples were:

Monomers I to IIIare shown in Ahlbrecht, Brown and Smith, US. Patent No.2,803,615.

Monomer IV is shown in Ahlbrecht, Reid and Husted, US. Patent No.2,642,416.

Monomer V is shown in the copending application of Ahlbrecht and Smith,Serial No. 677,229, filed August 9, 1957, now abandoned, but refiled ascontinuation S.N. 274,920, now Patent No. 3,102,103.

The procedure employed to prepare the polymers in ampoules was thefollowing sequence of steps:

(a) Charging the reactants to a heavy-walled Pyrex glass ampoule.

(b) Removing oxygen from the ampoule by freezing the contents of theampoule in liquid air, and evacuating it to a pressure of less than 0.01mm. mercury.

(c) Sealing the degrassed ampoule.

(d) Warming the sealed ampoule until the contents were melted.

(e) Polymerizing the contents by placing the ampoule in an end-overendrotor in a water bath at 50 C. for 16 hours.

The procedure employed to prepare the polymers in screw cap bottlesequipped with self-sealing rubber gaskets was to charge the reactantsand to flush the bottle with a stream of oxygen-free nitrogen gas priorto scaling the bottles and to polymerize the contents in an end-over-endrotator in a water bath at C. for the specified period of time.

The reaction mixture in each instance contained 100 parts of monomer,126 part of distilled water, 54 parts acetone, 0.2 part potassiumpersulfate, and emulsifier and mercaptan modifier, if any, asindicated.

The cotton fabrics were treated by immersing them in an aqueous pad bathcontaining a dimethylol ethyleneurea resin, an alkanolaminehydrochloride and polymers in the concentrations indicated andthereafter curing them for 10 minutes at about 150 C. The wool fabricswere treated by immersing them in an aqueous pad bath containing 4%isobutyl alcohol and 0.25% sodium acetate, and polymers at theconcentrations indicated, and thereafter curing them for 10 minutes atabout 150 C.

The water repellency of the treated fabrics was measured by StandardTest No. 2252, published in the 1952, Technical Manual and Yearbook ofthe American Association of Textile Chemists and Colorists, vol. XXVIII,page 136. The spray rating is expressed on a 0 to 100 scale, wherein 100is the highest possible rating.

The oil repellency test is based on the different penetrating propertiesof two hydrocarbon liquids, mineral oil and n-heptane. Mixtures of thesetwo liquids are miscible in all proportions and show penetratingproperties which increase with an increase in the n-heptane content ofthe mixture.

The oil repellency rating numbers were chosen to correspond with theA.A.T.C.C. Standard Spray Ratings which are now in use for testing waterrepellent finishes.

1 Percent by volume. I No holdout to mineral oil.

To measure o-il repellency of a treated fabric, 8" x 8" swatches are cutand placed fiat on a table. A drop of each mixture is gently placed ontothe surface of the fabric. The number corresponding to that mixturecontaining the highest percentage heptane which does not penetrate orwet the fabric after three minutes contact is considered the oilrepellency rating of the sample.

The treated fabric samples were dry cleaned three times withperchloroethylene containing a soap in commercial dry cleaningequipment. Because of the adverse elfect due to the soap residue on thedry cleaned fabrics, the spray rating tests were omitted.

The treated cotton fabrics were laundered three times in a 9 pound load,agitating, automatic washer machine using water at F. and a commercialdetergent, dried for 20 minutes at F., and ironed at 325 F. before beingtested and recorded as the washing rating.

EXAMPLE I This example shows the preparation of segmented andhomogeneous copolymers of monomer II and methyl vinyl ketone.

A. Segmented cOpolymer of monomer II and methyl vinyl ketone Methylvinyl ketone was polymerized to 84% conversion in 20% dioxane solutionin admixture with benzoyl peroxide for 45 hours at 50 C. The resultingpolymethyl vinyl ketone (3.3 grams) and 3.3 grams of monomer II werecharged to a heavy-walled Pyrex glass ampoule as a solution in 22 gramsof dioxane. The contents were frozen in liquid air. The tube was thenevacuated and sealed. The sealed ampoule was attached to a rock-ingplatform and subjected to ultraviolet irradiation from a 275 wattsunlamp placed 12 inches above the ampoule for 30 hours at 75 C. Thereaction product was a clear viscous solution and a solid phase. Thesolution was added to methanol to precipitate a polymer which afterwashing with methanol and drying in a vacuum at 60 C. weighed 2.5 gramsand was a hard, horny polymer. Elemental analysis of this polymer showedthat 7.5% monomer II had been grafted to the polymethyl vinyl ketone.(The homopolymer of monomer II is insoluble in dioxane.)

Aluminum panels coated with this segmented copolymer from a dioxanesolution had excellent oil and water repellency.

A 1% solution of the segmented copolymer in dioxane had a surfacetension of 24.2 dynes/cm., as measured with a Du Nouey Tensiometer. Theknown surface tension of dioxane is 36.9 dynes/ cm.

B. Homogeneous copolymers of monomers II and methyl 1 vinyl ketoneHomogeneous copolymers of methyl vinyl ketone and monomer II wereprepared in an ampoule by charging 10 grams of the monomer mixture, 20grams acetone and 0.08 gram benzoyl peroxide and reacting the mixturefor 20 hours. The monomer mixtures contained (a) 95 to 5, (b) 75 to 25,and (c) 50 to 50 parts by weight of methyl vinyl ketone and monomer II,respectively, for copolymers A, B and C. The resulting reaction mixtures9 were all clear, viscous solutions from which the copolymers wereprecipitated with methanol, washed and dried. The properties of hehomogenous copolymers were as follows:

Homogeneous Physical Percent Surface copolymer Characteristics MonomerII Tension 1 Combined A Hard, horny 3.8 36.2 B do 26 32. C Hard, brittle50 26.7

This example illustrates the preparation of homogenous and segmentedcopolymers of monomer II and butadiene.

A. Homogenozzs copolymer of 96 parts monomer II and 4 parts butadieneMonomer II (9.6 grams) and butadiene (0.4 gram) were polymerized in anampoule as described above in the presence of 0.5 gram C F SO NH(CH N(CH-HCl (emulsifier A) and 003 gram tertiary dode yl mercaptan. Theresulting latex, which represented 83% conversion to stably emulsifiedcopolymer, was employed to treat cotton and wool fabrics in a pad bathat the indicated concentration. The observed results are tabulated inTable I. The product obtained in this experiment was a powdery resinwhich was insoluble in benzene.

It will be noted in the table that the initial repellency properties ofthe fabrics treated with this product were excellent and the repellencyproperties remained after 3 commercial dry cleanings.

B. Homogeneous copolymer of 50 parts monomer II and 50 parts butadiene A4 ounce screw cap bottle was charged with 12.5 grams of monomer II, 31.5grams water, 13.5 grams acetone, 1.25 grams emulsifier A, 0.05 grampotassium persulfate, 0.075 gram tertiary dodecyl mercaptan, and 0.075gram n-octyl mercaptan. Butadiene was then added in excess and thebottle sealed when all but 12.5 grams of butadiene had flashed off.After a reaction period in a water bath for 18 hours at 50 C., a milky,stable latex containing 22.4 percent polymer solids (63% conversion to asuitably emulsified copolymer) was obtained.

A clear, tacky, flexible rubber was recovered from the latex which wassoluble in both xylene hexafluoride and benzene and gave clear, viscoussolutions in each.

The latex was used to treat wool fabrics and results obtained aretabulated in Table I. Excellent oil ratings were obtained but sprayratings were poor and the treatment obtained from this product was notdurable to commercial dry cleaning.

C. Segmented copolymer 0] 50 parts monomer 11 and 50 parts polybutadieneA 4 ounce screw cap bottle was charged with 31.5 grams water, 4.7 gramsacetone, 1.25 grams emulsifier A, 0.05 gram potassium persulfate, 0.125gram tertiary dodecyl mercaptan, and 0.125 gram n-octyl mercaptan.Butadiene was then added in excess and the bottle sealed when all but12.5 grams of butadiene had flashed ofi. After a reaction period in awater bath for 25.5 hours at 50 C., 97 percent conversion topolybutadiene having a molecular weight exceeding 2500 was accomplished.

Monomer II (12.5 grams) and 8.8 grams acetone were added to the latex.After an additional reaction period in a water bath for 15.5 hours at 50C., a stable, milky 1% latex containing 29 percent polymer solids,representing 81% total conversion to latex polymer, was obtained.

A soft, white, opaque, tack-free, putty-like solid polymer was separatedfrom the latex by coagulation with methanol. Over of the polymer wassoluble in benzene. Polybutadiene, as made by the above process, iscompletely soluble in benzene and completely insoluble in xylenehexaflnoride, whereas the homopolymer of monomer II is completelyinsoluble in benzene and completely soluble in xylene hexafluoride.

By analysis it was determined that the polymer recovered from thebenzene solution contained 54 percent combined monomer II units bondedto the polybutadiene pre-polymer. In this segmented copolymerapproximately 50% by weight of the A segment was fluorine derived fromthe perfluorooctyl group of monomer II.

This segmented copolymer, when applied to wool fabrics, imparted goodinitial repellency properties which were durable to dry cleaning asshown in Table I and the results were clearly superior to those obtainedwith the homogenous copolymer of the same monomer weight ratios asdescribed in IIB above.

D. Segmented copolymer having 50 parts homogeneous copolymer A segments(96 parts monomer II and 4 parts butadiene) and 50 parts polybutadiene Bsegments A 16 ounce screw cap bottle Was charged with 112.5 grams water,37.5 grams acetone, 2.5 grams emulsifier A,

0.1 gram potassium persulfate, and 0.2 gram tertiary dodecyl mercaptan.Butadiene was then added in excess and the bottle sealed when all but 50grams of the butadiene had flashed 01f. After reaction in a 50 C. waterbath for 23.5 hours, 80 percent conversion to polybutadiene wasaccomplished.

To grams of this latex (30 grams polybutadiene) in a 16 ounce screw capbottle Were added 28.8 grams monomer H, 16.2 grams acetone, 48.8 gramswater, 0.03 gram potassium persulfate, and 0.06 gram tertiary dodecylmercaptan. Butadiene was then added in excess and the bottle sealed whenall but 1.2 grams of butadiene had flashed 01f. After reactionin a waterbath at 50 C. for 19 hours, 89% total conversion to stably emulsifiedproduct containing segmented copolymer was obtained. The product, whichwas soluble in benzene, was similar in appearance to the 50:50 segmentedcopolymer described in IIC above.

When this segmented copolymer was applied to wool fabrics, results wereobtained which were equivalent to those obtained with the 50:50segmented copolymer (IIC above) and the 96:4 homogeneous copolymer (HAabove) and greatly improved over those obtained with the 50:50homogeneous copolymer (IIB above).

The results of this example show that the A segment can be a homogeneouscopolymer containing the requisite amount of a units.

This example demonstrates that the segmented copolymers possessproperties different from either the fiuorinated homopolymer or mixturesof homopolymers of the 'fluorinated and non-fiuorinated components.

A. Homopolymer of monomer II Monomer II grams) was polymerized in anampoule as described above in the presence of 0.5 gram of emusifier A toform a homopolymer which was a brittle resinous material. It is noted inTable II that this homopolymer gives cotton and wool treatments havinginferior initial oil repellency and inferior durability 'to dry cleaningand-laundering when compared to the segmented copolymer described inTable H. The cotton twills were treated in a pad bath containing noadditive.

B. Mixed Izomopolymers of monomer II and chloroprene prene clearlydemonstrates that a segmented copolymer was obtained.

D. Segmented copolymer of monomer II and chloroprene Chloroprene (5grams) and 5- grams of monomer H were polymerized in an ampoule asdescribed above in the presence of 0.5 gram of emulsifier A and 0.02gram of tertiary dodecyl mercaptan to form a product representing 77%conversion to stably emulsified polymer containing segmented copolymer.This material was employed to treat cotton, wool and nylon fabrics asshown in Table II. Cotton twill cloth (1) was treated in a pad bathcontaining no additive. Cotton twill cloth (2) was treated in a pad bathcontaining additives. The wool and nylon fabrics were treated in anaqueous pad bath containing 4% isobutyl alcohol and 0.12% sodiumacetate.

The performance of this segmented copolymer (HID) on fabrics isvirtually indistinguishable from the segmented copolymer IIIC, and farsuperior to HIA and IIIB. No durability was observed with the treatmentbased on the homopolymers of Examples IIIA and IIIB but the durabilityof the treatments based on the products in H10 and IIID was excellent.

TABLE 11 Initial Washing Percent Rating Dry Rating Polymer FabricPolymer Cleaning in Bath Rating, Oil

Oil Spray Oil Spray A Cotton twill 1 70 Wool polyester blend 1 90 Woolgabardineun 1 100 B Wool gabardine. 0. 5 100 Cotton print cloth. 1 70 CCotton twill 1 100 Cotton print cloth. 1 100 D Cotton twill 0. 5 90Cotton twill (1) l 90 Cotton twill (2) 1 90 Wool gabardine 0. 5 100+\Nool flannel. 0. 5 100+ Wool polyester blend 0. 5 100+ Nylon 0. 5 100containing 0.5% polychloroprene and 0.5% homopolymer EXAMPLE IV ofmonomer H.

C. Segmented copolymer of monomer II and Chloroprene A 250 milliliter3-neck flask fitted with a stirrer and equipment for purging withoxygen-free nitrogen was charged as follows:

After 2 hours reaction at 50 C. 86% of the chloroprene was converted tostably emulsified polymer. Monomer II (25 grams) was then added to theflask and the reaction continued -for 4.5 hours at which time 83% of thetotal monomer was converted to stably emulsified latex polymercontaining segmented copolymer.

Table H shows the oil and spray ratings for this segmented copolymerwhen applied to cotton fabrics from a pad bath containing 1% polymer,urea-formaldehyde resins and organic salt catalyst. The supioi'performance obtained with this product when compared with the mixedhomopolymers of monomer II and chloro- A series of products containingsegmented copolymers were prepared as described above by polymerizingchloroprene and monomer II in a heavy walled Pyrex glass ampoule in thepresence of 0.5 gram of emulsifier B to form latices representingapproximately conversion of the monomers charged to stably emulsifiedpolymer. The monomer charges to the ampoule were as follows:

Charge Monomer II Chloroprene (grams) (grams) A 5 5 B 3. 5 6. 5 C 3 7 D2. 5 7. 5 E 2 8 TABLE III Initial Percent Rating Dry Washing PolymerFabric Polymer Cleaning Rating, Oil

in Bath Rating, Oil

Oil Spray Cotton twill 1 100 100 100 80 Cotton print cloth 1 100 100 9080 Cotton twill 1 100+ 100 90 80 Cotton print cloth. 1 100+ 100 80 80Cotton twill 1 100+ 100 70 so Cotton print cloth 1 100+ 100 70 so Cottontwill 1 100 100 50 70 Cotton print cloth 1 10 100 50 70 Cotton twill 1100 so 70 Cotton print cloth 1 100 90 0 70 EXAMPLE V Initial RatingChloroprene (5 grams) and 5 grams of monomer II Fabric were polymerizedin an ampoule as described in the preson S pray ence of 0.5 gram ofemulsifier B and'0.04 gram tertiary dodecyl mercaptan to give 03%conversion to a stably Cotton twin: 100+ 90 emulsified product contarmngsegmented copolymer. g lg ardm 100+ 100 This product was employed totreat cotton fabrics at 1% amp 100+ concentration and the test resultsare shown below. Durability results in this case were observed afterthree commercial dry cleanings and 15 launderings to be as follows;EXAMPLE VII Chloroprene (5 grams) and monomer I (5 grams) werepolymerized in an ampoule as described above in the I presence of 0.5gram of emulsifier A and 0.04 gram of I t 1R t D W h m m a mg s itertlary dodecyl mercaptan. The resulting latex, WhlCh Fabric Rag firepresented a 78% conversion of the monomers to a on Spray on Spray 40stably emulsified product containing segmented copolymer, was employedto treat cotton and wool fabrics in a Cotton twill 100 100 100 so 100pad bath at the indicated concentrations. The observed Cotton Punt 100100 experimental results were as follows:

EXAMPLE V1 Percent Initial Rating Dry Fabric Polymer Cleaning in BathRating, oil T his example illustrates that segmented copolymer Oil Spraycompositions may be employed to treat fabrics from an organic solventsolution. g tt n Eng 1 100+ 70 100 A 5 gallon glass-lined kettle whichhas been flushed gg %?,;g f 8:? 1881' 5 ,3 igg with oxygen-free nitrogenwas charged as follows: W001 polyester blen 0- 100 100 Grams Monomer II1770 Emulsifier A 177 n-Octyl mercaptan 10.7 EXAMPLE VIII Tort-dodecylmercaptan 10.6 This example demonstrates the superior properties ofDistilled water 4460 the segmented copolymer over the homopolymer of theAcetone 1910 fluorine-containing monomer, particularly in regard to Thekettle was then flushed with nitrogen again and chloroprene (1770 grams)and potassium persulfate (K S O (7.1 grams) added with stirring. Aftermaintaining the kettle at 50 C. for 9 hours, 9360 gramsdry cleaningdurability. Y

A. Homopolymer of monomer III Monomer III (10 grams) was polymerized inan ampoule as described above in the presence of 0.5 gram emulsifier A.The resulting latex represented conversion to stably emulsified product.The homopolymer was a soft, flexible plastic.

Wool fabrics were treated with this polymer at pad bath-concentrationsof 0.5 and 0.25%. The latter level is comparable in the amount offluorine-containing polymer used with 0.5% of the 50:50 monomerIIIzchloroprene segmented copolymer described below. Results aretabulated in Table IV.

Chloroprene grams) and 5 grams of monomer III were polymerized in aheavy walled Pyrex glass ampoule as described above in the presence of0.5 gram of emulsi- EXAMPLE X Monomer V (1 gram) and 1 gram ofchloroprene were fierA and 0.02 gram of tertiary dodecyl mercaptan. The5 polymerized in an ampoule as described above in the resulting latex,which represented an 83% conversion of presence of 0.1 part ofemulsifier A. The results 0bthe monomers to a stably emulsified productcontaintamed by treating cotton fabrics with these segmented ingsegmented copolymer, was employed to treat wool copolymers at /2%concentration were as follows: fabrics and the measured resultstabulated in Table IV. The copolymer was an opaque, tack-free rubber.

TABLE Iv Percent InitialRating Dry Polymer Fabric Polymer Cleaning inBath Rating,

Oil Spray Oil A Wool gabardine 0.5 100+ 100 80 Woolllannel 0.5 100+ 9000 Wool polyester blend 0. 5 100 100 100 Wool gabardine- Wool flannel0.25 100 90 70 Wool polyester blend 0.25 100 100 80 B Wool gabar 'ne 0.5100+ 100 100 Wool flannel 0.5 100+ 100 100 Wool polyester blend 0. 5 100100 100 EXAMPLE IX This example also illustrates the superiority of theFabric mmalRating washing Rat-mg segmented copolymers over thehomopolymer of an a monomer, particularly in regard to dry cleaning andSpray Spray laundering durability.

Cottontw 1l1 100+ 100 90 so A. Homopolymer of monomer IV Cotton Drlllt010th 100 90 80 Monomer IV (10 grams) was polymerized in an ampoule asdescribed above in the presence of 0.5 gram EXAMPLE XI emulsifier A. Theproduct was a brittle, resinous material. The results obtained bytreating cotton and wool A natural f latex contalnlng 62% S01E15 Was f bi are Shown in Table aerated by tumbling a half-filled bottle of a latexfor two days and opening the bottle periodically to introduce air.

Segmented czpolymer parts monomer IV 40 Hydroperoxide groups wereintroduced into the rubber parts 6 oroprene ma'crornolecule in thismanner.

A product containing segmented copolymer was pre- 'I he aerated naturalrubber latex (equivalent to 20 pared by polymerizing 12.5 grams ofmonomer IV and grams of rubber solids), 20 grams of monomer II, 50.412.5 grams chloroprene in a 4 ounce screw cap bottle in grams water,21.6 grams acetone, 0.002 gram ferrous su l the presence of 1.25 gramsemulsifier A to a latex repre- 45 fate and 0.2 gram triethylenetetraminewere charged toa Sentiug 99% conversion to stably emulsified polymer. 16ounce screw cap bottle. The bottle was flushed with The product was anopaque, tough, tack-free rubber. oxygen-free nitrogen, sealed and shakenfor 10 minutes Cotton and wool fabrics were treated with the polymer atroom temperature whereupon monomer I1 polymerized d h resuns are b l t di T bl V, and the latex coagulated. The reaction mixture was washed withmethanol dried mixed with benzene and mer IV 1 z g gg 'g ig 2;; i 1 igf5O shaken overnight. A benzene insoluble fraction contamp p ing 23% ofmonomer II was obtained. This insoluble Monomer IV (6.3 grams) and 18.8grams of chlorofraction was masticated on a rubber mill whereupon theprene were polymerized in the same manner as the coproduct was observedto become soluble in benzene and polymer in B above to a latexrepresenting 93% converxylene 'hexafluoride. Masticated natural rubberis insolusion to stably emulsified product containing segmented coble inxylene hexafl-uoride and soluble in benzene, wherepolymer. The polymerwas similar-in appearance to the as the homopolymer of monomer H issoluble in xylene copolymer B above. Results obtained on cotton and woolhexafluoride and insoluble in benzene. fabrics are shown in Table V. Afilm made of the solubilizcd product containing seg- TABLE V InitialW'ashing Percent Rating Dry Rating Polymer Fabric Polymer Cleaning,

in Bath Oil Oil- Spray Oil Spray A Cotton print cloth 1 Wool gabardine0.5 WoclflanneL- 0.5 100+ Wool tweed. 0.5 90 B Cotton print cloth. 1 100Wool gabardine 0.5 100+ Woolflannel 0.5 100+ Wool tweed 05 100+ C Cottonrint cloth 1 100 Wool ga ardine 0.5 100 Wool fiannel 0.5 90 Wool tweed0.5 100 follows:

Polymer Fabric Oil Rating Spray Rating Segmented Wool gabardinc 100 80Wool flannel- 90 80 Cotton twilL. 50 80 3 :1 blend Wool gabardin 7 80Wool fianneL 80 70 Cotton twill 70 EXAMPLE XII The following monomersand emulsifier were charged into a 16 ounce screw cap bottle andpolymerized as described above for 16 hours:

Grams Monomer II 50 Chloroprene 50 CgF17SOzN C2H5 CH2COOK (emulsifier Alatex corresponding to 86% conversion to stably emul sified polymer wasobtained.

Samples of 50 pound unbleached kraft paper were treated with a latex ofthe product containing segmented copolymers (0.25 to 1% by weight) ofthis example and demonstrated resistance to penetration by turpentine.

Solutions (0.5%) of this polymer in 1,1,1-trichloroethane were employedto treat suede, vegetable tanned, and other leathers. In each instancethe leather became water and oil resistant.

Pelt bats were treated before and after blocking with a 0.25%1,1,1-trichloroethane solution of the segmented copolymers of thisexample. Water and oil repellency was imparted to the hats by thistreatment.

Microballoons which are used to reduce gasoline evaporation in storagetanks were coated with about 2% by weight of the segmented copolymer ofthis example. The treated balloons were not wetted by gasoline to thesame extent as the untreated balloons and in this manner the evaporationof gasoline was materially reduced.

Glass fiber filters became water and oil repellent upon being treatedwith a 0.5% solution of the segmented copolymer of this example in a1,1,1-trichloroethane solution.

Many polyvinyl acetate latices utilized as protective coatings have poorleveling properties. For instance, when an aluminum panel is coated witha polyvinyl acetate latex the film formed has valleys and ridges whichare visible to the naked eye and has poor gloss. When a small amount ofthe segmented copolymers of this example is added to polyvinyl acetatelatex a uniform film results. Thus, the segmented copolymer has aleveling efiect upon the polyvinyl acetate, in addition to impartingexcellent oil resistance and improved water resistance to coatings madefrom such blended formulations.

One-half percent by weight of solids of the segmented copolymer latex ofthis example was added to 3 commercially available white latex paints,i.e. a styrene-butadiene copolymer, an acrylic flat wall paint, and athixotropic acrylic base paint. Paint samples were shaken and thenbrushed onto plywood and etched aluminum panels and compared to controlpanels coated with the same paints containing no segmented copolymer.All panels were similar in appearance. The control coatings showed nooil repellency and were visibly stained 18 by a droplet of SAE No. 30lubricating oil whereas the panels coated with the paints containing thesegmented copolymers readily repelled oil, and droplets of a 60:40volume ratio of n-heptane and mineral oil did not spread on the treatedsurfaces.

A polyvinyl acetate emulsion to which had been added 2% by weight of thesegmented copolymer of this example based on polyvinyl acetate solidswas brushed on wallpaper samples so that the coating contained 5% byweight of total polymer blend based on the weight of the wallpaper.Droplets of SAE No. 30 lubricating oil remained as beads on thewallpaper coated with the .segmented copolymer whereas the dropletsspread on wallpaper treated with the polyvinyl acetate latex only. Thetreated samples were also superior in their resistance to soiling asobserved after subjecting the samples to various tests, e.g. placing thesamples side by side on a door panel and thereby subjecting both of themto heavy hand soiling.

EXAMPLE XIII A product containing segmented copolymer was prepared bypolymerizing 12.5 grams monomer II and 12.5 grams chloroprene in thepresence of 0.5 gram emulsifier A and 0.75 gram of an ethylene oxidecondensate of lauryl alcohol in a 4 ounce screw cap bottle. Afterreaction at 50 C. for 16 hours, 89% conversion to stably emulsifiedpolymer was obtained.

Treating 'baths were prepared which contained this segmented copolymer,a treating resin and catalyst. The treating bath in each instancecontained 1% of the polymer containing segmented copolymer, 15% byweight of the treating resin and 1.5% of the catalyst in water. Thefabric treated in each bath was a blend of rayon, polyester fiber,acrylic fiber and mohair in the weight ratio of 45 :43110z3. The fabricwas treated by padding the fabric at 40 pounds nip pressure andsubsequently drying and curing for 10 minutes at 150 C. The samples werethen laundered three times in an automatic washing machine and electricdryer. Table VI shows the results obtained as to oil and waterrepellency before and after laundering 'by various combinations of knowntextile treating resins and catalysts.

TABLE VI Initial Rating Washing Rating Resin 1 Catalyst 2 Oil Spray OilSpray 1 Resins:

A. Urea-formaldehyde resin. B. Urea formaldehyde resin. C.Melamine-ionnaldehyde resin. D. Glycol-acetal resin. E.'Iriazine-forrnaldehyde resin. 2 Catalysts:

A. Organic salt. B. Acid salt of an inorganic amine. C. Inorganic salt.

EXAMPLE XIV Styrene (40 gms.) and bromotrichloromethane (0.2 gm.) werecharged to a glass ampoule, frozen, degassed, thawed, refrozen andsealed under vacuum. After 17 hours reaction time using ultravioletlight initiation, the contents of the ampoule were a viscous liquid.This liquid was dissolved in benzene and precipitated and Washed withmethanol. After drying, polystyrene (14 gms.) was recovered.

Polystyrene (5 gms.), prepared as described above, and monomer II (5gms.) and dioxane (20 gms.) were charged to a glass ampoule and sealedas above. After 15 hours reaction under ultraviolet light irradiationthe contents of the ampoule was a milky liquid. The resulting polymerwas precipitated with methanol, redispersed in methyl chloroform, andreprecipitated and washed in methanol. After drying 8.2 gms. of polymerwere recovered (82% yield). Of this 8.2 grams, 78% was soluble in methylchloroform. Fluorine analysis showed this portion of the product tocontain 17.4% fluorine indicating a block copolymer composition of 65:35styrene:monomer II. A one percent solution of this block copolymer inmethyl chloroform was applied to upholstery fabrics. After dryingminutes at 150 C., oil repellencies of 100+ and spray ratings of 80 to90 were obtained.

The portion of the product not soluble in methyl chloroform was solublein xylene hexafluoride and contained 48% fluorine.

EXAMPLE XV Monomer II gms.), triethyl amine (210 gms.) andazobisisobutyronitrile (0.15 gm.) were charged to a 16 oz. screw capbottle, flushed With-oxygen free nitrogen, sealed and rotatedend-over-end in a 60 C. water bath for 24 hours. At the end of this timemost of the product had precipitated from solution. The precipitatedpolymer was dissolved in xylene hexafluoride and precipitated withmethanol. The triethylamine solution was also precipitated in methanol.The combined precipitates were filtered, washed with methanol and dried.A yield of 6.8 gms. of the homopolymer of monomer II, softening at about65 C. and melting at about 110 C. was obtained. The homopolymer (3gms.), acrylonitrile (3 gms.), benzene (9 gms.), Xylene hexafiuoride (9gms.) and azobisisobutyronitrile (0.012 gm.) were charged to a glassampoule, sealed under vacuum and tumbled in a 60 C. water bath for 16hours. At the end of this time the resulting polymer had precipitatedfrom the solution. After washing with benzene and drying, a polymer(4.65 gms.) was obtained which was 76% soluble in dimethyl formamide.The dimethyl formamide soluble portion contained 13% fluorine indicatinga block copolymer composition of 74:26 acrylonitrilezmonomer II, whichsoftened at about 150170 C. and decomposed above 200 C. A film of theblock copolymer cast from the dimethyl formamide solution was hard andscuff resistant and exhibited excellent oil repellency.

EXAMPLE XVI The homopolymer of Example XV (3 gms.), ethyl acrylate (2.25gms.), acrylonitrile (0.75 gm.), benzene (9 gms.), xylene hexafluoride(9 gms.) and azobisisobutyronitrile (0.012 gm.) were reacted for 16hours at 60 C. The resulting polymer (3.98 gms.) was dried. This productwas 60% soluble in dimethyl formamide and the methyl formamide solublefraction contained 11.4% fluorine indicating a block copolymercontaining 23% of Monomer II derived from the homopolymer prepolymer.The block copolymer was a fairly tough, flexible plastic. A film of thematerial exhibited good oil and water repellency and excellent scuffresistance.

EXAMPLE- XVII Through a short column of silica gel, Monomer IV (4.9gms.) was drained into a flamed glass ampoule and frozen in liquid air.In a similar manner, styrene (6.9 gms.) was added to the same ampouleand frozen in liquid air. The ampoule was then connected to a highvacuum apparatus and, while under vacuum and still frozen, 10 ml. of asolution of 0.4 gm. of sodium naphthalene in tetrahydrofuran were added.The entire contents of the ampoule were frozen in liquid air and theampoule sealed under vacuum. The bottom stratum in the ampoule, monomerIV, was kept frozen in liquid air while the other ingredients wereallowed to come slowly to room temperature. Polymerization of thestyrene began on thawing as evidenced by deep red colorization, localheat evolution and viscosity increase. When the polymerization of thestyrene was apparently complete, monomer IV was allowed to thaw. Onvigorous shaking, a small amount of monomer IV was diffused through abarrier of solid polystyrene which had formed at the interface into thesupernatant viscous solution of polystyrene in tetrahydrofuran. MonomerIV proceeded to block polymerize onto the polystyrene as evidenced by afading of the red color and a further increase in viscos ity. Theampoule was opened and the liquid contents precipitated in methanol. Theprecipitate was filtered, washed and dried. The resulting polymercontained 5.3% fluorine indicating a block copolymer composition of 91:9styrenezmonomer IV. The block copolymer was completely soluble inbenzene and insoluble in xylene hexafiuoride. A film of the polymer washard, brittle and clear. It exhibited excellent oil and water repellentproperties for use in the treatment of textiles.

EXAMPLE XVIII A cotton fabric was padded in an aqueous dispersioncontaining the following ingredients: dimethylol ethylene urea (5parts), ethylene oxide condensation product of lauryl alcohol (0.05part), dispersible melamine-formaldehyde condensation product (2 parts),ammonium salt accelerator (1 part), magnesium chloride (1 part),segmented copolymer (.75 part) prepared as described in Example XIII,and water (90.20 parts). The resulting fabric had oil repellency andspray ratings of 100.

EXAMPLE XIX A polyester-cotton blend was padded in aqueous dispersioncontaining the following ingredients: dimethylol ethylene urea (3parts), dispersible melamine-formaldehyde condensation product (2parts), ethylene oxide'condensation product of lauryl alcohol (0.01part), magnesium chloride 1.0 parts), segmented copolymer (.75 part)prepared as described in Example XIH, and Water (93.25 parts). Thesample was padded so that the fabric retained 55% by weight of thepadding dispersion and dried for 7 minutes at 325 F. The resultingfabric had oil repellency and spray ratings of 100.

EXAMPLE XX Cotton fabric was padded in an aqueous dispersion containingthe following ingredients: dimethylol ethylene urea solution (3 parts),melamine-formaldehyde condensation product (3.2 parts), ethylene oxidecondensation product of lauryl alcohol (0.05 part), polyvinyl alcohol (1part), ammonium salt accelerator (1 part), magnesium chloride (1 part),segmented copolymer prepared as described in Example XIII (.75 part) andwater (90.0 parts). The sample was padded at 40 lbs. nip pressure, driedfor 2 minutes at 250 F. and cured for 1% minutes at 350 F. The resultingfabric had an initial oil repellency and spray rating of 100.

EXAMPLE XXI Cotton fabric was padded in an aqueous dispersion containingthe following ingredients: water soluble triazine-formaldehydecondensation product (5 parts), magnesium chloride (1 part), isobutylalcohol (4 parts), segmented copolymer (.9 part) prepared as describedin Example XIII, and water (89.1 parts). The sample was padded, driedand cured for 5 minutes at 350 F. The resulting fabric had initial oilrepellency and spray ratings of 100. After 5 launderings and pressings,the sample had an oil repellency of and a spray rating of 90.

EXAMPLE XXII Four cotton samples of varying texture were padded with anaqueous dispersion containing 3 parts by weight of Phobotex FTC, aproduct of Ciba Products Corp., Fair Lawn, N.J., and identified as acationic thermosetting resin, 0.75 part by weight of Catalyst RB, aproduct of Ciba Products Corp. and identified as an aluminum containingorganic acid catalyst, and .9 part by weight of a segmented copolymerprepared as described in Example 21 XIII and 95.35 parts by weight ofwater. The samples were nipped at 20 lbs. with varying degrees of wetpickup as indicated below and then cured for 10 minutes at 150 C.

The same cotton .fabrics were treated in exactly the same manner asindicated in Example XXIII above, except that the padding bathcontained, in addition to ingredients set forth in Example XXII, byweight of a water soluble triazine-formaldehyde condensate and 0.5% byweight of magnesium chloride as an accelerator. The initial oilrepellency and spray ratings for these samples were as follows:

Sample Oil Spray Rating Repellency It will be appreciated that thetreating agents and combinations thereof may vary with the type oftextile to be treated. The following combinations of proprietary andcommercially available chemicals have been found to be especially usefulin treating the indicated fabrics in a manner such that the fabricretains 70% by weight of the aqueous treating media.

Thus, the segmented copolymers first made possible by this inventionhave been found to be especially useful with thermosettable aminoplasts.Especially useful aminoplasts are triazine formaldehyde condensationproducts, some of which are water dispersible but the most preferred arewater-soluble, such as poly-methylol-melamines. It will also beappreciated that methylol groups in this type of product are commonlyetherified by reaction with aliphatic alcohols such as methanol,ethanol, isopropanol and so forth. Since the ether oxygen is attached toa carbon atom that is attached to a nitrogen atom, it is easy to convertback to the methylol group. Illustrative ethers (partial or total) arethe trimethyl ethers of hexa-methylol melamine and tri-methylolmelamine. Other suitable thermosettable aminoplasts are the condensationproducts of an aldehyde, preferably formaldehyde, and urea, thiourea,and cyclic substituted ureas such as ethylene-urea and triazones. Thethermosettable aminoplasts may be employed in combination with acidicaccelerators or catalysts, such as the salts of Weak bases and strongacids, i.e-. magnesium chloride, zinc chloride, aluminum chloride,ammonium chloride and tri-ethanol amine-hydrochloride.

We claim:

1. An aqueous composition suitable as a textile treating agent forrendering the textile oil repellent comprising a segmented copolymerselected from the group consisting of block and graft copolymerscomprising 05-80 percent by weight of at least one A segment comprisingat least four polymerized units of R P where P is a radical containing apolymerizable ethylenic group and R, is a perfluoroalkyl radical of theformula C F where n is at least 4; said A segment containing at least 30percent by weight of fluorine derived from said group; and 20-99.5percent by weight of at least one B segment which comprises at least 5consecutive monomeric units of a polymeriza ble ethylenicallyunsaturated monomer different from said fluorine-containing monomericunits; said B segment containing less than 10 percent by weight offluorine derived from said Rf, a thermosettable aminoplast aldehydecondensation product of a compound selected from the group consisting oftriazine, urea, thiourea and cyclic substituted urea, and water.

2. An aqueous composition suitable as a textile treating agent forrendering the textile oil repellent comprising a segmented copolymerselected from the group consisting of block and graft copolymerscomprising 05-80 percent by weight of at least one A segment comprisingat least four polymerized units of R P where P is a radical containing apolymerizable ethylenic group and R; is a perfiuoro alkyl radical of theformula C F where n is at least 4; said A segment containing at least 30percent by weight of fluorine derived from said group; and 2099.5percent by weight of at least one B segment which comprises at least 5consecutive monomeric units of a polymeriza ble ethylenicallyunsaturated monomer different from said fluorine-containing monomericunits; said B segment containing less than 10 percent by weight offluorine derived from said R a triazine-formaldehyde condensationproduct as the thermosettable aminoplast and Water.

3. The composition of claim 2 in which the triazineformaldehydecondensation product is Water soluble.

4. The composition of claim 2 in which the triazineformaldehydecondensation product is a melamine-formaldehyde condensation product.

5. An improved textile treating process for rendering a textile oilrepellent comprising padding a textile in an aqueous compositioncomprising a segmented copolyrner selected from the group consisting ofblock and graft copolymers comprising 0.5- percent by weight of at leastone A segment comprising at least four polymerized units of R P where Pis a radical containing a polymerizable ethylenic group and R, is aperfiuoroalkyl radical of the formula C E where n is at least 4; said Asegment containing at least 30 percent by weight of fluorine derivedfrom said group; and 2099.5 percent by weight of at least one B segmentwhich comprises at least 5 consecutive monomeric units of apolymerizable ethylenically unsaturated monomer different from saidfluorine-containing monomeric units; said B segment containing less than10 percent by weight of fluorine derived from said R a thermosettableaminoplast aldehyde condensation product of a compound selected from thegroup consisting of triazine, urea, thiourea and cyclic substitutedurea, and water, drying the fabric and heating the fabric to thermosetthe aminoplast resin.

References Cited by the Examiner UNITED STATES PATENTS 2,536,050 1/1951Pluck 260-29.4 2,888,420 5/ 1959 Sulzer et al. 260-29.4 3,068,18712/1962 Bolstad et al. 26029. 6

MURRAY TILLMAN, Primary Examiner.

JOHN C. BLEUTGE, Assistant Examiner.

1. AN AQUEOUS COMPOSITION SUITABLE AS A TESTILE TREATING AGENT FORRENDERING THE TEXTILE OIL REPELLENT COMPRISING A SEGMENTED COPOLYMERSELECTED FROM THE GROUP CONSISTING OF BLOCK AND GRAFT COPOLYMERSCOMPRISING 0.5-80 PERCENT BY WEIGHT OF AT LEAST ONE A SEGMENT COMPRISINGAT LEAST FOUR POLYMERIZED UNITS OF RFP WHERE P IS A RADICAL CONTAINING APOLYMERIZABLE ETHYLENIC GROUP AND RF IS A PERFLUOROALKYL RADICAL OF THEFORMULA CNF2N+1 WHERE N IS AT LEAST 4; SAID A SEGMENT CONTAINING ATLEAST 30 PERCENT BY WEIGHT OF FLUORINE DERIVED FROM SAID GROUP; AND20-99.5 PERCENT BY WEIGHT OF AT LEAST ONE B SEGMENT WHICH COMPRISES ATLEAST 5 CONSECUTIVE MONOMERIC UNITS; OF A POLYMERIZABLE ETHYLEMICALLYUNSATURATED MONOMER DIFFERENT FROM SAID FLUORINE-CONTAINING MONOMERICUNITS; SAID B SEGMENT CONTAINING LESS THAN 10 PERCENT BY WEIGHT OFFLUORINE DERIVED FROM SAID RF A THERMOSETTABLE AMINOPLAST ALDEHYDECONDENSATION PRODUCT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OFTRIAZINE, UREA, THIOUREA AND CYCLIC SUBSTITUTED UREA, AND WATER.